JP3746337B2 - Method for preparing solid titanium catalyst component for olefin polymerization and method for producing polyolefin - Google Patents

Description

【００５２】
上記式中、Ｒ¹¹は置換または非置換の炭化水素基を示し、Ｒ¹²、Ｒ¹⁵、Ｒ¹⁶は、置換もしくは非置換の炭化水素基または水素原子を示し、Ｒ¹³、Ｒ¹⁴は、置換もしくは非置換の炭化水素基または水素原子を示し、好ましくはその少なくとも一方は置換または非置換の炭化水素基である。またＲ¹³とＲ¹⁴とは互いに連結されて環状構造を形成していてもよい。炭化水素基Ｒ¹¹〜Ｒ¹⁶が置換されている場合の置換基は、Ｎ、Ｏ、Ｓなどの異原子を含み、たとえば、Ｃ−Ｏ−Ｃ、ＣＯＯＲ、ＣＯＯＨ、ＯＨ、ＳＯ₃Ｈ、−Ｃ−Ｎ−Ｃ−、ＮＨ₂ などの基を有する。
【００５３】
このような多価カルボン酸エステルとしては、具体的には、
コハク酸ジエチル、コハク酸ジブチル、メチルコハク酸ジエチル、α-メチルグルタル酸ジイソブチル、メチルマロン酸ジエチル、エチルマロン酸ジエチル、イソプロピルマロン酸ジエチル、ブチルマロン酸ジエチル、フェニルマロン酸ジエチル、ジエチルマロン酸ジエチル、ジブチルマロン酸ジエチル、マレイン酸モノオクチル、マレイン酸ジオクチル、マレイン酸ジブチル、ブチルマレイン酸ジブチル、ブチルマレイン酸ジエチル、β-メチルグルタル酸ジイソプロピル、エチルコハク酸ジアルリル、フマル酸ジ-2-エチルヘキシル、イタコン酸ジエチル、シトラコン酸ジオクチルなどの脂肪族ポリカルボン酸エステル、
1,2-シクロヘキサンカルボン酸ジエチル、1,2-シクロヘキサンカルボン酸ジイソブチル、テトラヒドロフタル酸ジエチル、ナジック酸ジエチルなどの脂環族ポリカルボン酸エステル、
フタル酸モノエチル、フタル酸ジメチル、フタル酸メチルエチル、フタル酸モノイソブチル、フタル酸ジエチル、フタル酸エチルイソブチル、フタル酸ジn-プロピル、フタル酸ジイソプロピル、フタル酸ジn-ブチル、フタル酸ジイソブチル、フタル酸ジn-ヘプチル、フタル酸ジ-2-エチルヘキシル、フタル酸ジn-オクチル、フタル酸ジネオペンチル、フタル酸ジデシル、フタル酸ベンジルブチル、フタル酸ジフェニル、ナフタリンジカルボン酸ジエチル、ナフタリンジカルボン酸ジブチル、トリメリット酸トリエチル、トリメリット酸ジブチルなどの芳香族ポリカルボン酸エステル、
3,4-フランジカルボン酸などのヘテロ環ポリカルボン酸エステルなどが挙げられる。
【００５４】
また多価カルボン酸エステルの他の例としては、アジピン酸ジエチル、アジピン酸ジイソブチル、セバシン酸ジイソプロピル、セバシン酸ジn-ブチル、セバシン酸ジn-オクチル、セバシン酸ジ-2-エチルヘキシルなどの長鎖ジカルボン酸のエステルなどを挙げることができる。
【００５５】
本発明の方法により調製されたオレフィン重合用固体状チタン触媒成分は、下記周期律表第Ｉ族〜第III族から選択される金属を含む有機金属化合物触媒成分、および必要に応じて有機ケイ素化合物などの電子供与体と組み合わせてオレフィン重合用触媒として用いることができる。
【００５６】
このようなオレフィン重合用触媒としては、
（ａ）前記固体状チタン触媒成分と、
（ｂ）有機アルミニウム化合物触媒成分と、
（ｃ）Ｓｉ−Ｏ−Ｃ結合を有する有機ケイ素化合物触媒成分とからなるオレフィン重合用触媒がある。
【００５７】
図１に、本発明に係る固体状チタン触媒成分の調製工程の一例を表した説明図を示す。
有機金属化合物触媒成分としては、たとえば有機アルミニウム化合物、Ｉ族金属とアルミニウムとの錯アルキル化物、II族金属の有機金属化合物などを用いることができる。
【００５８】
有機アルミニウム化合物としては、たとえば下記一般式で表される有機アルミニウム化合物を例示することができる。
Ｒ^a _n ＡｌＸ_3-n
（式中、Ｒ^a は炭素原子数が１〜１２の炭化水素基を示し、Ｘはハロゲン原子または水素原子を示し、ｎは１〜３である。）
上記一般式において、Ｒ^a は炭素原子数が１〜１２の炭化水素基、たとえばアルキル基、シクロアルキル基またはアリール基であるが、具体的には、メチル基、エチル基、n-プロピル基、イソプロピル基、イソブチル基、ペンチル基、ヘキシル基、オクチル基、シクロペンチル基、シクロヘキシル基、フェニル基、トリル基などである。
【００５９】
このような有機アルミニウム化合物としては、具体的には以下のような化合物が挙げられる。
トリメチルアルミニウム、トリエチルアルミニウム、トリイソプロピルアルミニウム、トリイソブチルアルミニウム、トリオクチルアルミニウム、トリ（2-エチルヘキシル）アルミニウム、トリデシルアルミニウムなどのトリアルキルアルミニウム；
イソプレニルアルミニウムなどのアルケニルアルミニウム；
ジメチルアルミニウムクロリド、ジエチルアルミニウムクロリド、ジイソプロピルアルミニウムクロリド、ジイソブチルアルミニウムクロリド、ジメチルアルミニウムブロミドなどのジアルキルアルミニウムハライド；
メチルアルミニウムセスキクロリド、エチルアルミニウムセスキクロリド、イソプロピルアルミニウムセスキクロリド、ブチルアルミニウムセスキクロリド、エチルアルミニウムセスキブロミドなどのアルキルアルミニウムセスキハライド；
メチルアルミニウムジクロリド、エチルアルミニウムジクロリド、イソプロピルアルミニウムジクロリド、エチルアルミニウムジブロミドなどのアルキルアルミニウムジハライド；
ジエチルアルミニウムハイドライド、ジイソブチルアルミニウムハイドライドなどのアルキルアルミニウムハイドライドなど。
【００６０】
また有機アルミニウム化合物として、下記一般式で表される化合物を用いることもできる。
Ｒ^a _n ＡｌＬ_3-n
（式中、Ｒ^a は上記と同様であり、Ｌは−ＯＲ^b 基、−ＯＳｉＲ^c ₃ 基、−ＯＡｌＲ^d ₂ 基、−ＮＲ^e ₂ 基、−ＳｉＲ^f ₃ 基または−Ｎ（Ｒ^g ）ＡｌＲ^h ₂ 基であり、ｎは１〜２であり、Ｒ^b 、Ｒ^c 、Ｒ^d およびＲ^h はメチル基、エチル基、イソプロピル基、イソブチル基、シクロヘキシル基、フェニル基などであり、Ｒ^e は水素原子、メチル基、エチル基、イソプロピル基、フェニル基、トリメチルシリル基などであり、Ｒ^f およびＲ^g はメチル基、エチル基などである。）
このような有機アルミニウム化合物のなかでは、
Ｒ^a _n Ａｌ（ＯＡｌＲ^d ₂ ）_3-n で表される化合物、たとえば
Ｅｔ₂ＡｌＯＡｌＥｔ₂ 、（iso-Ｂｕ）₂ＡｌＯＡｌ（iso-Ｂｕ）₂ などが好ましい。
【００６１】
Ｉ族金属とアルミニウムとの錯アルキル化物としては、一般式
Ｍ¹ ＡｌＲ^j ₄
（但し、Ｍ¹ はＬｉ、ＮａまたはＫを示し、Ｒ^j は炭素原子数が１〜１５の炭化水素基を示す）
で表される化合物を例示でき、具体的には、ＬｉＡｌ（Ｃ₂Ｈ₅）₄、ＬｉＡｌ（Ｃ₇Ｈ₁₅）₄などを挙げることができる。
【００６２】
II族金属の有機金属化合物としては、
一般式 Ｒ^k Ｒ^l Ｍ²
（式中、Ｒ^k 、Ｒ^l は炭素原子数が１〜１５の炭化水素基またはハロゲンを示し、互いに同一でも異なっていてもよいが、いずれもハロゲンである場合は除く。Ｍ² はＭｇ、ＺｎまたはＣｄである）
で表される化合物を例示でき、具体的には、ジエチル亜鉛、ジエチルマグネシウム、ブチルエチルマグネシウム、エチルマグネシウムクロリド、ブチルマグネシウムクロリドなどを挙げることができる。
【００６３】
これらの有機金属化合物触媒成分は、１種単独で、または２種以上組み合わせて用いることができる。
また、このような有機金属化合物触媒成分と共に、必要に応じて電子供与体（Ｆ）を用いることができる。電子供与体（Ｆ）としては、Ｓｉ−Ｏ−Ｃ結合を有する有機ケイ素化合物などを挙げることができる。
【００６４】
Ｓｉ−Ｏ−Ｃ結合を有する有機ケイ素化合物としては、たとえば下記一般式（ｉ）で表す化合物を挙げることができる。
Ｒ^p _n Ｓｉ（ＯＲ^q ）_4-n … （ｉ）
（式中、Ｒ^p およびＲ^q は炭化水素基であり、０＜ｎ＜４である）
上記のような一般式で示される有機ケイ素化合物としては、具体的には、トリメチルメトキシシラン、トリメチルエトキシシラン、ジメチルジメトキシシラン、ジメチルジエトキシシシラン、ジイソプロピルジメトキシシラン、t-ブチルメチルジメトキシシラン、t-ブチルメチルジエトキシシラン、t-アミルメチルジエトキシシラン、ジフェニルジメトキシシラン、フェニルメチルジメトキシシラン、ジフェニルジエトキシシラン、ビスo-トリルジメトキシシラン、ビスm-トリルジメトキシシラン、ビスp-トリルジメトキシシラン、ビスp-トリルジエトキシシラン、ビスエチルフェニルジメトキシシラン、ジシクロヘキシルジメトキシシラン、シクロヘキシルメチルジメトキシシラン、シクロヘキシルメチルジエトキシシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、ビニルトリメトキシシラン、メチルトリメトキシシラン、n-プロピルトリエトキシシラン、デシルトリメトキシシラン、デシルトリエトキシシラン、フェニルトリメトキシシラン、γ-クロルプロピルトリメトキシシラン、メチルトリエトキシシラン、エチルトリエトキシシラン、ビニルトリエトキシシラン、t-ブチルトリエトキシシラン、n-ブチルトリエトキシシラン、iso-ブチルトリエトキシシラン、フェニルトリエトキシシラン、γ-アミノプロピルトリエトキシシラン、クロルトリエトキシシラン、エチルトリイソプロポキシシラン、ビニルトリブトキシシラン、シクロヘキシルトリメトキシシラン、シクロヘキシルトリエトキシシラン、2-ノルボルナントリメトキシシラン、2-ノルボルナントリエトキシシラン、2-ノルボルナンメチルジメトキシシラン、ケイ酸メチル、ケイ酸エチル、ケイ酸ブチル、トリメチルフェノキシシラン、メチルトリアリロキシ(allyloxy)シラン、ビニルトリス（β-メトキシエトキシシラン）、ビニルトリアセトキシシラン、ジメチルテトラエトキシジシロキサン；
シクロペンチルトリメトキシシラン、2-メチルシクロペンチルトリメトキシシラン、2,3-ジメチルシクロペンチルトリメトキシシラン、シクロペンチルトリエトキシシラン；
ジシクロペンチルジメトキシシラン、ビス（2-メチルシクロペンチル）ジメトキシシラン、ビス（2,3-ジメチルシクロペンチル）ジメトキシシラン、ジシクロペンチルジエトキシシラン；
トリシクロペンチルメトキシシラン、トリシクロペンチルエトキシシラン、ジシクロペンチルメチルメトキシシラン、ジシクロペンチルエチルメトキシシラン、ヘキセニルトリメトキシシラン、ジシクロペンチルメチルエトキシシラン、シクロペンチルジメチルメトキシシラン、シクロペンチルジエチルメトキシシラン、シクロペンチルジメチルエトキシシランが用いられる。
【００６５】
このうちエチルトリエトキシシラン、n-プロピルトリエトキシシラン、t-ブチルトリエトキシシラン、ビニルトリエトキシシラン、フェニルトリエトキシシラン、ビニルトリブトキシシラン、ジフェニルジメトキシシラン、フェニルメチルジメトキシシラン、ビスp-トリルジメトキシシラン、p-トリルメチルジメトキシシラン、ジシクロヘキシルジメトキシシラン、シクロヘキシルメチルジメトキシシラン、2-ノルボルナントリエトキシシラン、2-ノルボルナンメチルジメトキシシラン、フェニルトリエトキシシラン、ジシクロペンチルジメトキシシラン、ヘキセニルトリメトキシシラン、シクロペンチルトリエトキシシラン、トリシクロペンチルメトキシシラン、シクロペンチルジメチルメトキシシランなどが好ましく用いられる。
【００６６】
また、これら有機ケイ素化合物以外に用いることができる電子供与体（Ｆ）としては、窒素含有化合物、他の酸素含有化合物、燐含有化合物などを挙げることができる。
【００６７】
窒素含有化合物として具体的には、2,6-置換ピペリジン類、2,5-置換ピペリジン類、置換メチレンジアミン類、置換イミダゾリジン類などが挙げられる。
【００６８】
酸素含有化合物として具体的には、2,6-置換テトラヒドロピラン類、2,5-置換テトラヒドロピラン類などが挙げられる。
また燐含有化合物として具体的には、亜リン酸エステル類が挙げられる。
【００６９】
これらの電子供与体（Ｆ）は、１種単独で、または２種以上組み合わせて用いることができる。
【００７０】
このようなオレフィン重合用触媒を用いて重合することができるオレフィンとしては、炭素原子数が２〜２０のα−オレフィン、たとえばエチレン、プロピレン、1-ブテン、1-ペンテン、1-ヘキセン、4-メチル-1- ペンテン、1-オクテン、1-デセン、1-ドデセン、1-テトラデセン、1-ヘキサデセン、1-オクタデセン、1-エイコセンなどを挙げることができる。
【００７１】
重合においては、これらのオレフィンを単独で、あるいは組み合わせて使用することができる。さらにスチレン、アリルベンゼン等の芳香族ビニル化合物、ビニルシクロヘキサンなどの脂環族ビニル化合物、シクロペンテン、シクロヘプテン、ノルボルネン、5-メチル-2-ノルボルネン、テトラシクロドデセン、2-メチル-1,4,5,8- ジメタノ-1,2,3,4,4a,5,8,8a-オクタヒドロナフタレンなどの環状オレフィン、6-メチル1,6-オクタジエン、7-メチル-1,6-オクタジエン、6-エチル-1,6-オクタジエン、6-プロピル-1,6-オクタジエン、6-ブチル-1,6-オクタジエン、6-メチル-1,6-ノナジエン、7-メチル-1,6-ノナジエン、6-エチル-1,6-ノナジエン、7-エチル-1,6-ノナジエン、6-メチル-1,6-デカジエン、7-メチル-1,6-デカジエン、6-メチル-1,6-ウンデカジエン、イソプレン、ブタジエンなどのジエン類などの共役ジエンや非共役ジエンのような多不飽和結合を有する化合物を重合原料として用いることもできる。
【００７２】
重合は溶解重合、懸濁重合などの液相重合法あるいは気相重合法のいずれにおいても実施できる。
【００７３】
重合に際して、前記（ａ）固体状チタン触媒成分は、重合容積１リットル当り（ａ）固体状チタン触媒成分中のチタン原子に換算して、通常は約０．０００１〜５０ミリモル、好ましくは約０．００１〜１０ミリモルの量で用いられる。また、（ｂ）有機アルミニウム触媒成分は、重合系中のチタン原子１モルに対し、（ｂ）有機アルミニウム触媒成分に含まれるアルミニウム原子が、通常約１〜２０００モル、好ましくは約２〜５００モルとなるような量で用いられる。さらに（ｃ）有機ケイ素化合物は、（ｂ）有機アルミニウム触媒成分中のアルミニウム原子１モル当り、通常約０．００１〜５０モル、好ましくは約０．０１〜２０モルとなるような量で用いられる。
【００７４】
重合時に水素を用いると、メルトフローレートの大きいポリオレフィンが得られ、水素添加量によって得られるポリオレフィンの分子量を調節することができる。
【００７５】
反応条件は、液相重合法を行う場合には、重合温度は、通常、約−５０〜２００℃、好ましくは約２０〜１００℃であり、重合圧力は、通常、常圧〜１００ｋｇ／ｃｍ² 、好ましくは約２〜５０ｋｇ／ｃｍ² に設定される。気相重合法を行う場合には、重合温度は、通常、約−５０〜２００℃、好ましくは約２０〜１００℃であり、重合圧力は、通常、常圧〜１００ｋｇ／ｃｍ² 、好ましくは約２〜５０ｋｇ／ｃｍ² に設定される。
【００７６】
重合は回分式、半連続式、連続式のいずれの方法においても行うことができる。
【００７７】
【発明の効果】
本発明の固体状チタン触媒成分の調製方法は、固体状チタン触媒成分を調製する場合に、溶液状のチタン化合物としてチタン化合物を８８〜９９重量％、ハロゲン含有炭化水素を含む炭化水素を１〜１２重量％の割合で含有するチタン化合物混合液を用いているので、単位触媒当たりの活性が高いオレフィン重合用固体状チタン触媒成分が得られる。
【００７８】
また、溶液状のマグネシウム化合物と溶液状のチタン化合物とを接触させる工程において固体生成物に担持されなかったチタン化合物を含む溶液、および／または、固体生成物と溶液状のチタン化合物とを接触させる工程において固体状チタン触媒成分に担持されなかったチタン化合物を含む溶液を蒸留して前記のような組成としたものをチタン化合物混合液として用いると、チタン化合物の再利用が図れ、経済的に有利である。
【００７９】
本発明のポリオレフィンの製造方法は、前記のような固体状チタン触媒成分を含むオレフィン重合用触媒を用いているので、高い重合活性でオレフィンを重合することができる。
【００８０】
【実施例】
以下、実施例に基づいて本発明をさらに具体的に説明するが、本発明はこれら実施例に限定されるものではない。
【００８１】
なお、本実施例において四塩化チタン混合液の組成は、図２に示すような装置を用いて分離した炭化水素をガスクロマトグラフィーで測定することにより行った。四塩化チタンの純度は、四塩化チタン混合液の重量から炭化水素の重量を減じた残りを四塩化チタンの重量として求めた。図２は、四塩化チタン混合液の組成を求めるときに用いられる装置を示す概略説明図であり、１はコンデンサー、２は丸底フラスコ、３は氷水、４は冷却水循環ポンプ、５はペリスターポンプ、６はスターラーを示す。
(1) 乾燥した２００ｍｌの丸底フラスコにトルエンを約２０ｍｌ入れる。
(2) 試料１０ｍｌをホールピペットで採取し丸底フラスコに入れる。
(3) 図２に示すようにフラスコとコンデンサーとを継ぎ氷冷する。
(4) 冷却水循環ポンプのスイッチを入れ、コンデンサー内に氷水を循環させる。
(5) コンデンサーが冷えたら、ペリスターポンプのスイッチを入れ、１分あたり２ｍｌの量で純水の滴下を開始する。（SPEED＝×１５、CONTROL＝３〜５、POWER＝Ｒ）
(6) 水を滴下していくと、黄褐色の固形物が生成する。この状態で、フラスコとコンデンサーとの継ぎ目を手で持ってゆっくりと攪拌する。（スターラーをセットして攪拌いてもよい。）
(7) 更に水を滴下すると、固形物は溶解し白濁した液となる。白濁がでなくなれば反応を終了する。
(8) 丸底フラスコの内容物を１００ｍｌの分液ロートＡに移し、トルエン１０ｍｌで丸底フラスコ内壁を洗い分液ロートＡに移す。
(9) 分液ロートＡを振盪し、静置分離後、水相は別の分液ロートＢに移し、トルエン相を５０ｍｌメスフラスコに移す。
(10)分液ロートＡにトルエン１０ｍｌを入れ、内壁を洗い分液ロートＢに移して振盪する。
(11)静置分離後、トルエン相をトルエンの入った５０ｍｌのメスフラスコに入れる。
(12)トルエン相の入った５０ｍｌのメスフラスコにp-キシレンを約０．５ｍｌ添加し、下記の条件でガスクロマトグラフィーの測定を行った。
【００８２】

【００８３】
【実施例１】
固体状チタン触媒成分（Ａ−１）の調製
０．５ｍ³ の反応器へ、2-エチルヘキシルアルコール ９８．５ｋｇとデカン７８．３ｋｇと塩化マグネシウム ２４ｋｇとを装入し、１４０℃で均一溶液とした後、無水フタル酸 ５．６ｋｇを装入し、さらにこれを室温まで冷却して液状のマグネシウム化合物（ｍ−１）を得た。
【００８４】
次に、１ｍ³ の反応器に表１に示す組成を有する四塩化チタン混合液（１）０．３ｍ³ を装入し、−２０℃はで降温して、上記マグネシウム化合物（ｍ−１）を１０３．２ｋｇ装入した。この四塩化チタン混合液（１）は、下記比較例２で貯槽（Ｄ）に保存された四塩化チタンを含む炭化水素を、ボトム温度６７．５℃、トップ温度５２．０℃、トップ圧力５０Ｔｏｒｒ、リフラックス量５００．１ｋｇ／時間の条件で蒸留することにより得た。
【００８５】
装入終了後、１１０℃に昇温し、ジイソブチルフタレート ８．８ｋｇを装入して、２時間保持した。反応終了後、液相部を抜き出して、貯槽（Ｄ）に保存し、固体部をフィルターに窒素で圧送して濾過した。
【００８６】
濾過後の固体部に少量の四塩化チタンを加えて１ｍ³ の反応器に圧送し、０．４ｍ³ の表１に示す組成を有する四塩化チタン混合液（１）を加えた。
なお、フィルターは１００℃、フェルターと１ｍ³ の反応器を連結する圧送ラインは９０℃に保持した。
【００８７】
次に、１ｍ³ の反応器内を１１０℃に昇温し、２０分間保持した後、液相部を上記と同様にフィルターに圧送して濾過した。濾過後、１ｍ³ の反応器に圧送し、６０℃のヘキサン ０．４ｍ³ での洗浄を３回繰り返した後、室温のヘキサンでの洗浄を上澄み液中にチタンが検知されなくなるまで行った。
【００８８】
このようにして得られた固体部をパドルドライヤーで乾燥し、表２に示すような組成を有する固体状チタン触媒成分（Ａ−１）を得た。
重合
内容積２リットルのオートクレーブに精製n-ヘキサン７５０ｍｌを装入し、４０℃、プロピレン雰囲気にてトリエチルアルミニウム０．７５ミリモル、シクロヘキシルメチルジメトキシシラン０．０７５ミリモルおよび固体状チタン触媒成分（Ａ−１）をチタン原子換算で０．００７５ミリモルＴｉ装入した。
【００８９】
さらに６０℃で水素２００ｍｌを導入し、７０℃に昇温した後これを２時間保持してプロピレン重合を行った。重合中の圧力は７ｋｇ／ｃｍ²-G に保った。
重合終了後、生成固体を含むスラリーを濾過し、白色粉末と液相部に分離した後、白色粉末を１０時間減圧乾燥して、重量と物性を測定した。また、液相部の一部を濃縮して、溶媒（n-ヘキサン）に可溶なポリマーの生成量を算出した。結果を表３に示す。
【００９０】
【実施例２】
固体状チタン触媒成分（Ａ−２）の調製
実施例１で得られた貯槽（Ｄ）に保存されたチタン化合物含有溶液（四塩化チタン純度８５重量％）を、ボトム温度６８．３℃、トップ温度５２．６℃、トップ圧力４６Ｔｏｒｒ、リフラックス量４７９．２ｋｇ／時間の条件で蒸留して、表１に示す組成を有する四塩化チタン混合液（２）を得た。
【００９１】
この四塩化チタン混合液（２）を実施例１で使用した四塩化チタン混合液（１）に代えて使用したこと以外は実施例１と同様にして固体状チタン触媒成分（Ａ−２）を調製した。固体状チタン触媒成分（Ａ−２）の組成を表２に示す。
【００９２】
重合
実施例１において固体状チタン触媒成分（Ａ−１）に代えて、前記固体状チタン触媒成分（Ａ−２）を用いたこと以外は、実施例１と同様にしてプロピレンを重合した。結果を表３に示す。
【００９３】
【実施例３】
固体状チタン触媒成分（Ａ−３）の調製
実施例２で得られた貯槽（Ｄ）に保存されたチタン化合物含有溶液（四塩化チタン純度８５重量％）を、ボトム温度７０．２℃、トップ温度５４．３℃、トップ圧力５２Ｔｏｒｒ、リフラックス量４４９．８ｋｇ／時間の条件で蒸留して、表１に示す組成を有する四塩化チタン混合液（３）を得た。
【００９４】
この四塩化チタン混合液（３）を実施例１で使用した四塩化チタン混合液（１）に代えて使用したこと以外は実施例１と同様にして固体状チタン触媒成分（Ａ−３）を調製した。固体状チタン触媒成分（Ａ−３）の組成を表２に示す。
【００９５】
重合
実施例１において固体状チタン触媒成分（Ａ−１）に代えて、前記固体状チタン触媒成分（Ａ−３）を用いたこと以外は、実施例１と同様にしてプロピレンを重合した。結果を表３に示す。
【００９６】
【実施例４】
固体状チタン触媒成分（Ａ−４）の調製
実施例３で得られた貯槽（Ｄ）に保存されたチタン化合物含有溶液（四塩化チタン純度８５重量％）を、ボトム温度６７．１℃、トップ温度４９．２℃、トップ圧力３０Ｔｏｒｒ、リフラックス量４８１．７ｋｇ／時間の条件で蒸留して、表１に示す組成を有する四塩化チタン混合液（４）を得た。
【００９７】
この四塩化チタン混合液（４）を実施例１で使用した四塩化チタン混合液（１）に代えて使用したこと以外は実施例１と同様にして固体状チタン触媒成分（Ａ−４）を調製した。固体状チタン触媒成分（Ａ−４）の組成を表２に示す。
【００９８】
重合
実施例１において固体状チタン触媒成分（Ａ−１）に代えて、前記固体状チタン触媒成分（Ａ−４）を用いたこと以外は、実施例１と同様にしてプロピレンを重合した。結果を表３に示す。
【００９９】
【実施例５】
固体状チタン触媒成分（Ａ−５）の調製
実施例４で得られた貯槽（Ｄ）に保存されたチタン化合物含有溶液（四塩化チタン純度８５重量％）を、ボトム温度６９．６℃、トップ温度５２．８℃、トップ圧力４７Ｔｏｒｒ、リフラックス量４８０．７ｋｇ／時間の条件で蒸留したものと、貯槽（Ｄ）に保存されたチタン化合物含有溶液とを等量ずつ混合して、表１に示す組成を有する四塩化チタン混合液（５）を得た。
【０１００】
この四塩化チタン混合液（５）を実施例１で使用した四塩化チタン混合液（１）に代えて使用したこと以外は実施例１と同様にして固体状チタン触媒成分（Ａ−５）を調製した。固体状チタン触媒成分（Ａ−５）の組成を表２に示す。
【０１０１】
重合
実施例１において固体状チタン触媒成分（Ａ−１）に代えて、前記固体状チタン触媒成分（Ａ−５）を用いたこと以外は、実施例１と同様にしてプロピレンを重合した。結果を表３に示す。
【０１０２】
【比較例１】
固体状チタン触媒成分（Ａ−６）の調製
実施例１で得られた貯槽（Ｄ）に保存されたチタン化合物含有溶液（四塩化チタン純度８５重量％）を蒸留せず、実施例１で使用した四塩化チタン混合液（１）に代えて使用したこと以外は実施例１と同様にして固体状チタン触媒成分（Ａ−６）を調製した。固体状チタン触媒成分（Ａ−６）の組成を表２に示す。
【０１０３】
重合
実施例１において固体状チタン触媒成分（Ａ−１）に代えて、前記固体状チタン触媒成分（Ａ−６）を用いたこと以外は、実施例１と同様にしてプロピレンを重合した。結果を表３に示す。
【０１０４】
【比較例２】
固体状チタン触媒成分（Ａ−７）の調製
実施例１で使用した四塩化チタン混合液（１）に代えて、純度が１００重量％の四塩化チタンを使用したこと以外は実施例１と同様にして固体状チタン触媒成分（Ａ−７）を調製した。固体状チタン触媒成分（Ａ−７）の組成を表２に示す。
【０１０５】
重合
実施例１において固体状チタン触媒成分（Ａ−１）に代えて、前記固体状チタン触媒成分（Ａ−７）を用いたこと以外は、実施例１と同様にしてプロピレンを重合した。結果を表３に示す。
【０１０６】
【実施例６】
固体状チタン触媒成分（Ａ−８）の調製
攪拌装置を具えた４つ口フラスコを充分に窒素置換し、室温（２６℃）で塩化マグネシウム４．８ｇを加えた。次いで、トルエン７５ｍｌを加えて、２００ｒｐｍで攪拌を開始し、クロロメチルオキシラン７．８５ｍｌを加え、さらにトリ-n-ブチルフォスフェート８．１８ｍｌを加えた。次に、攪拌数を３５０ｒｐｍとし、５０℃に昇温した。５０℃に２時間保持した後、無水フタル酸１．１８ｇを加え、さらに１時間５０℃に保持して、液状のマグネシウム化合物（ｍ−２）を得た。
【０１０７】
次に、−２３℃まで冷却した後、同温度で１時間にわたって、実施例１で用いたものと同一の四塩化チタン混合液（１）を滴下した。次に、４時間かけて８０℃まで昇温し、ジイソブチルフタレート３．３５ｍｌを加えた。同温度に１時間保持した後、濾過によって固体部を採取し、得られた固体部をトルエン１００ｍｌでの洗浄を２回行った。
【０１０８】
洗浄後の固体部をトルエン６０ｍｌで懸濁して、フラスコに戻し四塩化チタン混合液（１）４０ｍｌを加えた後、９０℃に昇温した。９０℃で１時間保持した後、濾過によって固体部を採取しトルエン６０ｍｌで再懸濁してフラスコに戻した。次に四塩化チタン混合液（１）を加えた後、９０℃に昇温して１時間保持した後に、濾過によって固体部を採取した。得られた固体部を1,2-ジクロロエタン１００ｍｌで洗浄した後、ヘキサン１００ｍｌでの洗浄を４回行って、固体状チタン触媒成分（Ａ−８）を得た。固体状チタン触媒成分（Ａ−８）の組成を表２に示す。
【０１０９】
重合
実施例１において固体状チタン触媒成分（Ａ−１）に代えて、前記固体状チタン触媒成分（Ａ−８）を用いたこと以外は、実施例１と同様にしてプロピレンを重合した。結果を表３に示す。
【０１１０】
【比較例３】
固体状チタン触媒成分（Ａ−９）の調製
実施例６で使用した四塩化チタン混合液（１）に代えて、純度が１００重量％の四塩化チタンを使用したこと以外は実施例６と同様にして固体状チタン触媒成分（Ａ−９）を調製した。固体状チタン触媒成分（Ａ−９）の組成を表２に示す。
【０１１１】
重合
実施例１において固体状チタン触媒成分（Ａ−１）に代えて、前記固体状チタン触媒成分（Ａ−９）を用いたこと以外は、実施例１と同様にしてプロピレンを重合した。結果を表３に示す。
【０１１２】
【表１】

【０１１３】
【表２】

【０１１４】
【表３】

【図面の簡単な説明】
【図１】 本発明に係る固体状チタン触媒成分の調製方法の一例を示す説明図である。
【図２】 四塩化チタン混合液の組成を求めるときに用いられる装置を示す概略説明図である。
【符号の説明】
１ … コンデンサー
２ … 丸底フラスコ
３ … 氷水
４ … 冷却水循環ポンプ
５ … ペリスターポンプ
６ … スターラー[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for preparing a solid titanium catalyst component used as a catalyst component of an olefin polymerization catalyst and a method for producing a polyolefin.
[0002]
TECHNICAL BACKGROUND OF THE INVENTION
Conventionally, as a catalyst used for producing an olefin polymer such as an α-olefin homopolymer or an ethylene / α-olefin copolymer, there is a catalyst containing a titanium compound supported on an active magnesium halide. Are known. As such an olefin polymerization catalyst, a catalyst comprising a solid titanium catalyst component and an organometallic compound catalyst component containing magnesium, titanium, halogen and a polycarboxylic acid ester as essential components is known.
[0003]
There have already been many proposals for the production method of solid titanium catalyst components containing magnesium, titanium, halogen and polyvalent carboxylic acid ester as essential components. A solid component formed by contacting a compound with a solution-like titanium compound in the presence of an electron donor is loaded with a polyvalent carboxylic acid ester to form a solid product. A method of forming a solid titanium catalyst component by contacting with a titanium compound is known. It is also known that a polymer having high stereoregularity can be produced in a high yield by using this solid titanium catalyst component during polymerization of an α-olefin having 3 or more carbon atoms.
[0004]
Under such circumstances, the inventors of the present invention have conducted intensive studies on a solid titanium catalyst component having further excellent polymerization activity. As a result, when preparing the solid titanium catalyst component by the above-described method, When a titanium compound mixture liquid containing a halogen-containing hydrocarbon in a specific ratio is used as the titanium compound component, the amount per unit catalyst is surprisingly higher than when a 100% pure titanium compound is used. The inventors have found that a solid titanium catalyst component having excellent activity per unit catalyst can be obtained because the amount of supported titanium increases, and the present invention has been completed.
[0005]
OBJECT OF THE INVENTION
The present invention has been made in view of the prior art as described above, and provides a method for preparing a solid titanium catalyst component capable of obtaining a solid titanium catalyst component for olefin polymerization having a high polymerization activity per unit catalyst. It aims at providing, and it aims at providing the manufacturing method of polyolefin using the solid titanium catalyst component obtained by this method.
[0006]
SUMMARY OF THE INVENTION
The method for preparing a solid titanium catalyst component for olefin polymerization according to the present invention comprises:
In preparing a solid titanium catalyst component containing titanium, magnesium and halogen as essential components by contacting (A) a magnesium compound and (B) a solution-like titanium compound,
The (B) solution-like titanium compound is characterized by using a titanium compound mixed solution composed of 88 to 99% by weight of a titanium compound and 1 to 12% by weight of a hydrocarbon containing a halogen-containing hydrocarbon.
[0007]
As a method for preparing such a solid titanium catalyst component for olefin polymerization, for example,
(A ′) a solid component produced by bringing a solution-like magnesium compound and (B) a solution-like titanium compound into contact with each other in the presence of (C) an electron donor, supporting a polyvalent carboxylic acid ester, In preparing a solid titanium catalyst component containing titanium, magnesium, halogen and a polyvalent carboxylic acid ester as essential components,
(B) a method using a titanium compound mixed liquid composed of 88 to 99% by weight of a titanium compound and 1 to 12% by weight of a hydrocarbon containing a halogen-containing hydrocarbon, as the solution-like titanium compound,
(A ') Formed by supporting polyvalent carboxylic acid ester on solid component produced by contacting solution-like magnesium compound and (B) solution-like titanium compound in the presence of (C) electron donor. In preparing a solid titanium catalyst component containing titanium, magnesium, halogen and polyvalent carboxylic acid ester as essential components by bringing the solid product thus obtained into contact with (B ′) a solution-like titanium compound.
Titanium compound comprising 88 to 99% by weight of a titanium compound and 1 to 12% by weight of a hydrocarbon containing a halogen-containing hydrocarbon as the (B) solution-like titanium compound and / or the (B ′) solution-like titanium compound. There is a method using a mixed solution.
[0008]
In the method for preparing a solid titanium catalyst component for olefin polymerization according to the present invention, a solid titanium catalyst component for olefin polymerization having a high polymerization activity per unit catalyst is obtained because the amount of titanium supported per unit catalyst is increased.
[0009]
The method for producing a polyolefin according to the present invention includes:
(A) a solid titanium catalyst component obtained by the above method;
(B) an organoaluminum catalyst component;
(C) an organosilicon compound catalyst component having a Si—O—C bond;
It is characterized by using an olefin polymerization catalyst comprising:
[0010]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, a method for preparing a solid titanium catalyst component for olefin polymerization and a method for producing a polyolefin according to the present invention will be specifically described.
[0011]
In the present invention, when preparing a solid titanium catalyst component containing titanium, magnesium and halogen as essential components by contacting (A) a magnesium compound with (B) a solution-like titanium compound,
As the (B) solution-like titanium compound, a titanium compound mixture composed of 88 to 99% by weight of a titanium compound and 1 to 12% by weight of a hydrocarbon containing a halogen-containing hydrocarbon is used.
[0012]
The titanium compound mixture used in the present invention comprises a titanium compound of 88 to 99% by weight, preferably 90 to 99% by weight, and a hydrocarbon containing halogen-containing hydrocarbons of 1 to 12% by weight, preferably 1 to 10% by weight. It is desirable to consist of.
[0013]
Examples of the titanium compound contained in the titanium compound mixture include a tetravalent titanium compound represented by the following formula.
Ti (OR)_nX_4-n
(Wherein R represents a hydrocarbon group, X represents a halogen atom, and n is 0 ≦ n ≦ 4)
As such a titanium compound, specifically,
TiCl_Four, TiBr_Four, TiI_FourTitanium tetrahalides such as;
Ti (OCH_Three) Cl_Three, Ti (OC₂H_Five) Cl_Three, Ti (On-C_FourH₉) Cl_Three, Ti (OC₂H_Five) Br_Three, Ti (O-iso-C_FourH₉) Br_ThreeTrihalogenated alkoxy titaniums such as;
Ti (OCH_Three)₂Cl₂, Ti (OC₂H_Five)₂Cl₂, Ti (On-C_FourH₉)₂Cl₂, Ti (OC₂H_Five)₂Br₂Dihalogenated dialkoxytitanium such as;
Ti (OCH_Three)_ThreeCl, Ti (OC₂H_Five)_ThreeCl, Ti (On-C_FourH₉)_ThreeCl, Ti (OC₂H_Five)_ThreeMonohalogenated trialkoxytitanium such as Br;
Ti (OCH_Three)_Four, Ti (OC₂H_Five)_Four, Ti (On-C_FourH₉)_Four, Ti (O-iso-C_FourH₉)_FourTi (O-2-ethylhexyl)_FourExamples thereof include tetraalkoxy titanium and the like.
[0014]
Among these, halogen-containing titanium compounds are preferable, titanium tetrahalides are more preferable, and titanium tetrachloride is particularly preferable. One of these titanium compounds may be contained in the titanium compound mixed solution, or two or more thereof may be contained.
[0015]
“Hydrocarbon containing halogen-containing hydrocarbon” contained in the titanium compound mixture is a mixture of halogen-containing hydrocarbon and hydrocarbon.
Specific examples of halogen-containing hydrocarbons include halogen-containing aliphatic hydrocarbons such as chloroethane, chloropropane, chlorobutane, chlorohexane, chloroheptane, chlorooctane, chlorononane, and chlorodecane; halogen-containing alicyclic hydrocarbons such as chlorocyclohexane Halogen-containing aromatic hydrocarbons such as chlorobenzene and chlorotoluene. A plurality of these halogen-containing hydrocarbons may be contained in hydrocarbons including halogen-containing hydrocarbons. It is desirable that the halogen-containing hydrocarbon is contained in the titanium compound mixture at a ratio of 0.01 to 3.0% by weight.
[0016]
Examples of the hydrocarbon include saturated aliphatic hydrocarbons, unsaturated aliphatic hydrocarbons, and aromatic hydrocarbons. Hydrocarbons having 4 to 16 carbon atoms are preferable, and saturated hydrocarbons having 4 to 16 carbon atoms are particularly preferable. Hydrocarbons are preferred. Examples of the saturated hydrocarbon having 4 to 16 carbon atoms include butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane and the like. Of these, saturated hydrocarbons having 5 to 14, preferably 6 to 12 carbon atoms are preferred. A plurality of these saturated hydrocarbons may be contained in saturated hydrocarbons including halogen-containing hydrocarbons.
[0017]
Examples of such a titanium compound mixture include 90 to 98.6% by weight of a titanium compound, 0.1 to 0.9% by weight of 2-chlorooctane, 0 to 0.4% by weight of hexane, and 0.8% of octane. The liquid mixture which consists of 7 to 4.5 weight%, nonane 0.1 to 0.5 weight%, and decane 0.5 to 3.7 weight% is mentioned.
[0018]
The titanium compound mixed solution may be a mixture of the titanium compound and a hydrocarbon containing a halogen-containing hydrocarbon so as to have the above composition, and prepares a solid titanium compound catalyst component as described later. The titanium compound-containing solution obtained at this time may be distilled to have the above composition.
[0019]
Specifically as a magnesium compound (A) used by this invention,
Magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, magnesium fluoride;
Alkoxy magnesium halides such as methoxy magnesium chloride, ethoxy magnesium chloride, isopropoxy magnesium chloride, butoxy magnesium chloride, octoxy magnesium chloride;
Allyloxy magnesium halides such as phenoxy magnesium chloride, methylphenoxy magnesium chloride;
Alkoxy magnesium such as ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, octoxy magnesium, 2-ethylhexoxy magnesium;
Examples include aryloxymagnesium such as phenoxymagnesium and dimethylphenoxymagnesium; magnesium carboxylates such as magnesium laurate and magnesium stearate, and inorganic acid salts such as magnesium carbonate, magnesium borate, and magnesium silicate. However, the magnesium compound may be a complex compound with another metal, a double compound, or a mixture with another metal compound. Furthermore, a mixture of two or more of these compounds may be used. Among these, magnesium halide, particularly magnesium chloride is preferable.
[0020]
In the present invention, the magnesium compound can be used as a liquid magnesium compound such as a solution-like magnesium compound or a magnesium compound suspension. When the magnesium compound is solid, it is dissolved in a solvent having a magnesium compound solubilizing ability to form a solution-like magnesium compound, or suspended in a medium not having the magnesium compound solubilizing ability to suspend the magnesium compound. Used as a liquid. When the magnesium compound is a liquid, it can be used as it is as a solution-like magnesium compound, which can be dissolved in a solvent having a magnesium compound solubilizing ability and used as a solution-like magnesium compound. In the present invention, the magnesium compound is preferably used as a solution-like magnesium compound.
[0021]
As a solvent having a magnesium compound solubilizing ability, for example, titanate can be used, and an electron donor (E) such as alcohol, aldehyde, amine, carboxylic acid and metal acid ester other than titanium can be used. These compounds may be used alone or in admixture of two or more.
[0022]
Examples of titanates include methyl orthotitanate, ethyl orthotitanate, n-propyl orthotitanate, i-propyl orthotitanate, n-butyl orthotitanate, i-butyl orthotitanate, and n-amyl orthotitanate. , Orthotitanate esters such as 2-ethylhexyl orthotitanate, n-octyl orthotitanate, phenyl orthotitanate, cyclohexyl orthotitanate; methyl polytitanate, ethyl polytitanate, n-propyl polytitanate, i-propyl polytitanate And polytitanate esters such as n-butyl polytitanate, i-butyl polytitanate, n-amyl polytitanate, 2-ethylhexyl polytitanate, n-octyl polytitanate, phenyl polytitanate, and cyclohexyl polytitanate.
[0023]
Specific examples of alcohols having solubilizing ability of magnesium compounds include methanol, ethanol, propanol, butanol, ethylene glycol, methyl carbitol, 2-methylpentanol, 2-ethylbutanol, n-heptanol, n-octanol, Aliphatic alcohols such as 2-ethylhexanol, decanol, dodecanol, tetradecyl alcohol, undecenol, oleyl alcohol, stearyl alcohol; cycloaliphatic alcohols such as cyclohexanol, methylcyclohexanol; benzyl alcohol, methylbenzyl alcohol, isopropylbenzyl alcohol, Aromatic alcohols such as α-methylbenzyl alcohol and α, α-dimethylbenzyl alcohol; alkoxy such as n-butyl cellosolve and 1-butoxy-2-propanol And the like aliphatic alcohols containing.
[0024]
Examples of the carboxylic acid include organic carboxylic acids having 7 or more carbon atoms such as caprylic acid, 2-ethylhexanoic acid, undecylenic acid, undecanoic acid, noneric acid, and octanoic acid.
[0025]
Examples of the aldehyde include aldehydes having 7 or more carbon atoms such as capric aldehyde, 2-ethylhexyl aldehyde, capryl aldehyde, and undecyl aldehyde.
[0026]
Examples of the amine include amines having 6 or more carbon atoms such as heptylamine, octylamine, nonylamine, decylamine, laurylamine, undecylamine, 2-ethylhexylamine and the like.
[0027]
Examples of the metal acid ester include zirconium tetraalkoxides such as zirconium tetramethoxide, zirconium tetraethoxide, zirconium tetrabutoxide, and zirconium tetrapropoxide.
[0028]
These titanic acid ester and electron donor (E) can be used together with an inert solvent, and specific examples of such an inert solvent include propane, butane, pentane, hexane, heptane, octane, decane, Aliphatic hydrocarbons such as dodecane and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride and chlorobenzene; Alternatively, a mixture thereof can be used.
[0029]
In the solution-like magnesium compound (A ′) in which the magnesium compound is dissolved in such a solvent, the magnesium compound is usually 0.1 to 20 mol / liter, preferably 0.5 to 5 with respect to the solvent. Contained in a mole / liter ratio.
[0030]
Examples of the medium having no magnesium compound solubilizing ability include the same hydrocarbons as the inert solvent, and aromatic hydrocarbons are preferable.
In the suspension in which the magnesium compound is suspended in the medium not having the solubilizing ability for the magnesium compound, the magnesium compound is usually 0.1 to 20 mol / liter, preferably 0. It is contained at a rate of 5 to 5 mol / liter.
[0031]
In the present invention, the magnesium compound and the titanium compound mixed solution are brought into contact with each other to prepare a solid titanium catalyst component containing titanium, magnesium and halogen as essential components. As described above, the magnesium compound is usually used in the form of a solution or a suspension.
[0032]
Specific methods for preparing the solid titanium catalyst component include, for example, the following methods.
(1) A method of preparing a solid titanium catalyst component containing titanium, magnesium and halogen as essential components by bringing a solution-like magnesium compound and a titanium compound mixed solution into contact with each other in the presence of an electron donor (C).
(2) A polycarboxylic acid ester is supported on a solid component produced by bringing a solution-like magnesium compound and a titanium compound mixed solution into contact with each other in the presence of an electron donor (C) to form titanium, magnesium, A method for preparing a solid titanium catalyst component containing halogen and a polyvalent carboxylic acid ester as essential components.
(3) The solid titanium catalyst component obtained in (2) is further brought into contact with a titanium compound mixed solution to prepare a solid titanium catalyst component containing titanium, magnesium, halogen, and polyvalent carboxylic acid ester as essential components. Method.
(4) Mg (OR¹)₂(However, R¹Is a method of preparing a solid titanium catalyst component containing titanium, magnesium and halogen as essential components by bringing a titanium compound mixed solution into contact with a magnesium compound suspension in which an alkyl group is suspended in a hydrocarbon. However, when the titanium compound contained in the titanium compound mixture is a compound that does not contain halogen, the titanium compound and the halogenating agent are brought into contact with each other in any step.
(5) Solution-like organomagnesium compound (for example, MgR² ₂, MgR²R^ThreeHowever, R², R^ThreeIs a method of preparing a solid titanium catalyst component containing titanium, magnesium and halogen as essential components by bringing a titanium compound mixture into contact with a hydrocarbon group having 1 to 20 carbon atoms. However, when the titanium compound contained in the titanium compound mixture is a compound that does not contain a halogen, a titanium compound that does not contain a halogen in any process, and SiX_Four, R^FourX (where X is halogen, R^FourIt is essential to contact a halogenating agent such as hydrocarbon).
(6) In (4) and (5), a solid titanium catalyst component containing titanium, magnesium, halogen and a polyvalent carboxylic acid ester as essential components is prepared by contacting the polyvalent carboxylic acid ester in any process. how to.
(7) In (4) to (6), a method for preparing a solid titanium catalyst component containing titanium, magnesium and halogen as essential components by contacting with an organic carrier or an inorganic carrier in any process.
(8) In the presence of a surfactant, titanium is used as a solid component obtained by quenching a suspension containing magnesium halide and alcohol complex particles in a molten state in a hydrocarbon to solidify the complex particles. A solid titanium catalyst containing titanium, magnesium, halogen, and polyvalent carboxylic acid ester as essential components by bringing the compound mixture into contact with the polyvalent carboxylic acid ester and supporting the titanium compound and polyvalent carboxylic acid ester on the solid component. A method of preparing the ingredients.
[0033]
Here, as the polyvalent carboxylic acid ester supported on the solid titanium catalyst component, a phthalic acid ester is preferable, and a phthalic acid diester is particularly preferable.
The amount of each of the above components used in preparing the solid titanium catalyst component varies depending on the preparation method and cannot be specified unconditionally. For example, the titanium compound is added as a titanium compound in the solution to a concentration of 0.001 per mol of the magnesium compound. The polyvalent carboxylic acid ester is used in an amount of 0.01 to 10 mol, preferably 0.1 to 5 mol, per mol of the magnesium compound. Used. The electron donor (C) is used in an amount of 0.01 to 5 mol, preferably 0.05 to 2 mol, per mol of the magnesium compound.
[0034]
The solid titanium catalyst component thus obtained contains magnesium, titanium and halogen as essential components. In this solid titanium catalyst component, the halogen / titanium (atomic ratio) is in the range of about 2 to 200, preferably about 4 to 100, and the magnesium / titanium (atomic ratio) is about 1 to 100, preferably about 2 to 2. It is desirable to be in the range of 50. When the polycarboxylic acid ester is contained, the polyvalent carboxylate ester / titanium (molar ratio) is desirably in the range of about 0.01 to 100, preferably about 0.2 to 10.
[0035]
In the present invention, it is preferable to employ the following method as a method for preparing the solid titanium catalyst component. Among these, it is preferable to adopt the method (2) from the viewpoint of polymerization activity.
(1) A polycarboxylic acid ester is supported on a solid component produced by contacting a solution-like magnesium compound (A ′) and a solution-like titanium compound (B) in the presence of an electron donor (C). And preparing a solid titanium catalyst component comprising titanium, magnesium, halogen and a polyvalent carboxylic acid ester as essential components.
(2) A polycarboxylic acid ester is supported on a solid component produced by contacting a solution-like magnesium compound (A ′) and a solution-like titanium compound (B) in the presence of an electron donor (C). In preparing a solid titanium catalyst component containing titanium, magnesium, halogen, and polyvalent carboxylic acid ester as essential components by bringing the solid product thus formed into contact with a solution-like titanium compound (B ′). A method for preparing a solid titanium catalyst component using a titanium compound mixed solution as the (B) solution-like titanium compound and / or the (B ′) solution-like titanium compound. In this case, it is preferable to use a titanium compound mixed solution for both the (B) solution-like titanium compound and the (B ′) solution-like titanium compound.
[0036]
The (B) solution-like titanium compound and the (B ′) solution-like titanium compound may be a titanium compound mixed solution having the same composition or a titanium compound mixed solution having different compositions. When the titanium compound mixed solution is used only for one of (B) the solution-like titanium compound and (B ′) the solution-like titanium compound, the other solution-like titanium compound includes the tetravalent titanium compound, Preferably, a halogen-containing titanium compound is used, more preferably titanium tetrahalide, and particularly preferably titanium tetrachloride.
[0037]
As a method for preparing a solid titanium catalyst component for olefin polymerization preferred in the present invention, more specifically,
(I) A polycarboxylic acid ester is supported on a solid component formed by contacting a solution-like magnesium compound (A ′) and a solution-like titanium compound (B) in the presence of an electron donor (C). To form a solid product.
(II) Further, the solid product is brought into contact with the solution-like titanium compound (B ′) to produce a solid titanium catalyst component.
[0038]
The step (I) for forming the solid product (solid titanium catalyst component) can be performed in the presence of the hydrocarbon solvent (D). The step (II) for producing the solid titanium catalyst component can be performed in the presence of a polyvalent carboxylic acid ester and / or an electron donor (C ′) and / or a hydrocarbon solvent (D ′). In this case, the polyvalent carboxylic acid ester used in step (I) and the polyvalent carboxylic acid ester used in step (II) may be the same or different, and the electron donor (C) and the electron donor The body (C ′) may be the same or different, and the hydrocarbon solvent (D) and the hydrocarbon solvent (D ′) may be the same or different.
[0039]
Here, hydrocarbon solvents (D) and (D ′) include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, methylcyclopentane, etc. Examples thereof include alicyclic hydrocarbons; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride and chlorobenzene, and mixtures thereof. The electron donors (C) and (C ′) will be described later.
[0040]
In the present invention, the titanium compound mixed solution as described above is used as the solution-like titanium compound (B) and / or (B ′). This titanium compound mixed solution is a step of forming a solid product (I ) And / or a titanium compound not supported on the solid titanium catalyst component obtained in the step (II) of generating the solid titanium catalyst component. It may be a purified titanium compound mixed solution obtained by distilling a solution containing the above, or may be a mixture of the purified titanium compound mixed solution and the liquid titanium compound so as to have the above composition. .
[0041]
In addition, the solution containing the titanium compound not supported on the solid product is obtained by bringing the solution-like magnesium compound, the titanium compound (solution-like titanium compound), and (C) the electron donor into contact with each other. When the solid product is prepared, (A ′) a solution-like magnesium compound, a titanium compound mixture, and (C) an electron donor may be contacted to prepare the solid product. It may occur. In addition, the solution containing the titanium compound not supported on the solid titanium catalyst component may be produced when the solid product and the titanium compound (solution titanium compound) are brought into contact with each other. It may be generated when the product and the titanium compound mixture are brought into contact with each other.
[0042]
The solution containing the titanium compound not supported on the solid product or the solid titanium catalyst component is usually a solution comprising about 85% by weight of the titanium compound and a plurality of hydrocarbons. The titanium compound mixture having the above composition is obtained by distillation under the conditions of a top temperature of 53 ° C., a top pressure of 47 Torr, and a reflux amount of 480 kg / hour.
[0043]
When the solid titanium catalyst component is prepared by such a method, the amount of the components (A ′), (B), (B ′), (C) and the polyvalent carboxylic acid ester used, the type, contact Depending on conditions, etc.
In the step (I) for forming a solid product, the polyvalent carboxylic acid ester is particularly preferably about 0.01 mol to about 5 mol, particularly preferably about 1 mol to 1 mol of the magnesium compound in the solution-like magnesium compound (A ′). Is used in an amount of about 0.1 mol to about 1 mol, and the solution-like titanium compound (B) is used in the component (B) with respect to 1 mol of the magnesium compound in the solution-like magnesium compound (A ′). In terms of the titanium compound, it is used in an amount of 0.1 mol to 1000 mol, particularly preferably 1 mol to 200 mol. The electron donor (C) is used in an amount of about 0.01 to 5 mol, particularly preferably about 0.05 to 2 mol, per 1 mol of the magnesium compound in the solution-like magnesium compound (A ′).
[0044]
In the step (II) of generating the solid titanium catalyst component, the solution-like titanium compound (B ′) is converted into the titanium compound in the component (B ′) with respect to 1 mol of the magnesium compound in the solid product. Thus, it is used in an amount of 0.1 mol to 1000 mol, particularly preferably 1 mol to 200 mol.
[0045]
The temperature at which each of the components is brought into contact is usually -70 ° C to 200 ° C, preferably -30 ° C to 150 ° C.
The solid titanium catalyst component thus obtained contains titanium, magnesium, halogen and polyvalent carboxylic acid ester.
[0046]
In the solid titanium catalyst component prepared in step (I) or step (II) as described above, the halogen / titanium (atomic ratio) is 2 to 100, preferably 4 to 90, and is a polyvalent carboxylic acid ester. / Titanium (molar ratio) is 0.01 to 100, preferably 0.2 to 10, and magnesium / titanium (atomic ratio) is 2 to 100, preferably 4 to 50.
[0047]
When preparing the solid titanium catalyst component as described above, the titanium compound is contained in a proportion of 88 to 99% by weight and the hydrocarbon containing a halogen-containing hydrocarbon is contained in a proportion of 1 to 12% by weight as the solution-like titanium compound component. When a titanium compound mixture is used, the amount of titanium compound supported per solid titanium catalyst component increases as compared with the case where a 100% pure titanium compound is used. A titanium catalyst component is obtained. Furthermore, the solution containing the titanium compound not supported on the solid product in the step of bringing the solution-like magnesium compound into contact with the solution-like titanium compound, and / or bringing the solid product and the solution-like titanium compound into contact with each other. When a solution containing the titanium compound not supported on the solid titanium catalyst component in the process is distilled and used as a titanium compound mixture, the titanium compound can be reused and economically advantageous. It is.
[0048]
Specific examples of the electron donors (C) and (C ′) used in the present invention include the following compounds.
Amines such as methylamine, ethylamine, dimethylamine, diethylamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, tributylamine, tribenzylamine;
Pyrroles such as pyrrole, methyl pyrrole and dimethyl pyrrole;
Pyrroline; pyrrolidine; indole; pyridines such as pyridine, methylpyridine, ethylpyridine, propylpyridine, dimethylpyridine, ethylmethylpyridine, trimethylpyridine, phenylpyridine, benzylpyridine, pyridine chloride;
Nitrogen-containing cyclic compounds such as piperidines, quinolines, isoquinolines;
Cyclic oxygenated compounds such as tetrahydrofuran, 1,4-cineole, 1,8-cineole, pinolefuran, methylfuran, dimethylfuran, diphenylfuran, benzofuran, coumaran, phthalane, tetrahydropyran, pyran, ditedropyran;
Phenols having 6 to 20 carbon atoms which may have a lower alkyl group such as phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol, naphthol;
Ketones having 3 to 15 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, acetylacetone, benzoquinone;
Aldehydes having 2 to 15 carbon atoms, such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, naphthaldehyde;
Methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, cyclohexanecarboxyl Ethyl acetate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl benzoate Ethyl, methyl anisate, n-butyl maleate, diisobutyl methylmalonate, di-n-hexylcyclohexenecarboxylate, diethyl nadic acid, diisopropyl tetrahydrophthalate, diethyl phthalate, diisobutyl phthalate, Organic acid esters having 2 to 30 carbon atoms, such as di-n-butyl phthalate, di-2-ethylhexyl phthalate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, and ethyl carbonate;
Acid halides having 2 to 15 carbon atoms such as acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid chloride, phthalic acid chloride;
Ethers having 2 to 20 carbon atoms, such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, anisole, diphenyl ether epoxy-p-menthane;
2-isopentyl-2-isopropyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2-cyclohexylmethyl-2-isopropyl- 1,3-dimethoxypropane, 2,2-diisopentyl-1,3-dimethoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclopentyl-2-isopropyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 1,2-bis-methoxymethyl-bicyclo- [2,2,1] -heptane, Diphenyldimethoxysilane, isopropyl-t-butyldimethoxysilane, 2,2-diisobutyl-1,3-dimethoxycyclohexane, 2-isopentyl-2-isopropyl-1,3-dimethoxycyclohexane, 9,9-dimethoxymethylfluorene Which diethers;
Acid amides such as acetic acid amide, benzoic acid amide, toluic acid amide;
Nitriles such as acetonitrile, benzonitrile and tolunitrile;
Organophosphorus compounds having a P—O—C bond such as trimethyl phosphite and triethyl phosphite;
Acid anhydrides such as acetic anhydride, phthalic anhydride, and benzoic anhydride are used.
[0049]
As the electron donors (C) and (C ′), an organosilicon compound represented by the general formula (i) as described later can also be used.
These electron donors can be used alone or in combination of two or more.
[0050]
Specific examples of the polyvalent carboxylic acid ester used in the present invention include the following compounds.
[0051]
[Chemical 1]

[0052]
In the above formula, R¹¹Represents a substituted or unsubstituted hydrocarbon group, R¹², R¹⁵, R¹⁶Represents a substituted or unsubstituted hydrocarbon group or a hydrogen atom, R¹³, R¹⁴Represents a substituted or unsubstituted hydrocarbon group or a hydrogen atom, preferably at least one of which is a substituted or unsubstituted hydrocarbon group. Also R¹³And R¹⁴And may be connected to each other to form a ring structure. Hydrocarbon group R¹¹~ R¹⁶Substituents in the case where is substituted include heteroatoms such as N, O, S, etc._ThreeH, -C-N-C-, NH₂It has groups such as.
[0053]
As such a polyvalent carboxylic acid ester, specifically,
Diethyl succinate, dibutyl succinate, diethyl methyl succinate, diisobutyl α-methylglutarate, diethyl methylmalonate, diethyl ethylmalonate, diethyl isopropylmalonate, diethyl butylmalonate, diethyl phenylmalonate, diethyl diethylmalonate, dibutyl Diethyl malonate, monooctyl maleate, dioctyl maleate, dibutyl maleate, dibutyl butyl maleate, diethyl butyl maleate, diisopropyl β-methylglutarate, diallyl ethyl succinate, di-2-ethylhexyl fumarate, diethyl itaconate, Aliphatic polycarboxylic acid esters such as dioctyl citraconic acid,
Alicyclic polycarboxylic acid esters such as diethyl 1,2-cyclohexanecarboxylate, diisobutyl 1,2-cyclohexanecarboxylate, diethyl tetrahydrophthalate, diethyl nadic acid,
Monoethyl phthalate, dimethyl phthalate, methyl ethyl phthalate, monoisobutyl phthalate, diethyl phthalate, ethyl isobutyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, phthalate Di-n-heptyl acrylate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, dineopentyl phthalate, didecyl phthalate, benzyl butyl phthalate, diphenyl phthalate, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, trimellit Aromatic polycarboxylic acid esters such as triethyl acid and dibutyl trimellitic acid,
And heterocyclic polycarboxylic acid esters such as 3,4-furandicarboxylic acid.
[0054]
Other examples of polycarboxylic acid esters include long chains such as diethyl adipate, diisobutyl adipate, diisopropyl sebacate, di-n-butyl sebacate, di-n-octyl sebacate, di-2-ethylhexyl sebacate Mention may be made of esters of dicarboxylic acids.
[0055]
The solid titanium catalyst component for olefin polymerization prepared by the method of the present invention includes an organometallic compound catalyst component containing a metal selected from Group I to Group III of the following periodic table, and, if necessary, an organosilicon compound It can be used as an olefin polymerization catalyst in combination with an electron donor.
[0056]
As such an olefin polymerization catalyst,
(A) the solid titanium catalyst component;
(B) an organoaluminum compound catalyst component;
(C) There is an olefin polymerization catalyst comprising an organosilicon compound catalyst component having a Si—O—C bond.
[0057]
FIG. 1 is an explanatory diagram showing an example of a preparation process of a solid titanium catalyst component according to the present invention.
As the organometallic compound catalyst component, for example, an organoaluminum compound, a complex alkylated product of a group I metal and aluminum, an organometallic compound of a group II metal, or the like can be used.
[0058]
As an organoaluminum compound, the organoaluminum compound represented by the following general formula can be illustrated, for example.
R^a _nAlX_3-n
(Wherein R^aRepresents a hydrocarbon group having 1 to 12 carbon atoms, X represents a halogen atom or a hydrogen atom, and n is 1 to 3. )
In the above general formula, R^aIs a hydrocarbon group having 1 to 12 carbon atoms, such as an alkyl group, a cycloalkyl group, or an aryl group. Specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an isobutyl group, a pentyl group, and the like. Group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group, tolyl group and the like.
[0059]
Specific examples of such organoaluminum compounds include the following compounds.
Trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tri (2-ethylhexyl) aluminum, tridecylaluminum;
Alkenyl aluminum such as isoprenyl aluminum;
Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dimethylaluminum bromide;
Alkylaluminum sesquichlorides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide;
Alkylaluminum dihalides such as methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride, ethylaluminum dibromide;
Alkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride.
[0060]
Moreover, the compound represented by the following general formula can also be used as an organoaluminum compound.
R^a _nAlL_3-n
(Wherein R^aIs the same as above, and L is -OR.^bGroup, -OSiR^c _ThreeGroup, -OAlR^d ₂Group, -NR^e ₂Group, -SiR^f _ThreeGroup or -N (R^g) AlR^h ₂A group, n is 1-2, R^b, R^c, R^dAnd R^hIs a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group, and the like;^eIs a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, a phenyl group, a trimethylsilyl group, etc., and R^fAnd R^gIs a methyl group, an ethyl group or the like. )
Among these organoaluminum compounds,
R^a _nAl (OAlR^d ₂)_3-nA compound represented by
Et₂AlOAlEt₂, (Iso-Bu)₂AlOAl (iso-Bu)₂Etc. are preferable.
[0061]
The complex alkylated product of Group I metal and aluminum has the general formula
M¹AlR^j _Four
(However, M¹Represents Li, Na or K, R^jRepresents a hydrocarbon group having 1 to 15 carbon atoms)
And specifically, LiAl (C₂H_Five)_Four, LiAl (C₇H₁₅)_FourAnd so on.
[0062]
As an organometallic compound of Group II metal,
General formula R^kR^lM²
(Wherein R^k, R^lRepresents a hydrocarbon group having 1 to 15 carbon atoms or a halogen, which may be the same or different from each other, except that they are all halogens. M²Is Mg, Zn or Cd)
And specifically include diethyl zinc, diethyl magnesium, butyl ethyl magnesium, ethyl magnesium chloride, butyl magnesium chloride, and the like.
[0063]
These organometallic compound catalyst components can be used singly or in combination of two or more.
Moreover, an electron donor (F) can be used as needed with such an organometallic compound catalyst component. Examples of the electron donor (F) include organosilicon compounds having a Si—O—C bond.
[0064]
Examples of the organosilicon compound having a Si—O—C bond include compounds represented by the following general formula (i).
R^p _nSi (OR^q)_4-n      (I)
(Wherein R^pAnd R^qIs a hydrocarbon group, 0 <n <4)
Specific examples of the organosilicon compound represented by the general formula as described above include trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, t-butylmethyldimethoxysilane, t -Butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis o-tolyldimethoxysilane, bism-tolyldimethoxysilane, bisp-tolyldimethoxysilane, Bis-p-tolyldiethoxysilane, bisethylphenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, ethyltrimethoxy Silane, ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyltriethoxy Silane, ethyltriethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, n-butyltriethoxysilane, iso-butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlorotriethoxysilane , Ethyltriisopropoxysilane, vinyltributoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2-norbornanetriethoxy Silane, 2-norbornanemethyldimethoxysilane, methyl silicate, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriallyloxysilane, vinyltris (β-methoxyethoxysilane), vinyltriacetoxysilane, dimethyltetra Ethoxydisiloxane;
Cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2,3-dimethylcyclopentyltrimethoxysilane, cyclopentyltriethoxysilane;
Dicyclopentyldimethoxysilane, bis (2-methylcyclopentyl) dimethoxysilane, bis (2,3-dimethylcyclopentyl) dimethoxysilane, dicyclopentyldiethoxysilane;
Tricyclopentylmethoxysilane, tricyclopentylethoxysilane, dicyclopentylmethylmethoxysilane, dicyclopentylethylmethoxysilane, hexenyltrimethoxysilane, dicyclopentylmethylethoxysilane, cyclopentyldimethylmethoxysilane, cyclopentyldiethylmethoxysilane, cyclopentyldimethylethoxysilane are used. .
[0065]
Of these, ethyltriethoxysilane, n-propyltriethoxysilane, t-butyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, vinyltributoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, bis p-tolyldimethoxy Silane, p-tolylmethyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, phenyltriethoxysilane, dicyclopentyldimethoxysilane, hexenyltrimethoxysilane, cyclopentyltriethoxysilane Silane, tricyclopentylmethoxysilane, cyclopentyldimethylmethoxysilane and the like are preferably used.
[0066]
Examples of the electron donor (F) that can be used in addition to these organosilicon compounds include nitrogen-containing compounds, other oxygen-containing compounds, and phosphorus-containing compounds.
[0067]
Specific examples of the nitrogen-containing compound include 2,6-substituted piperidines, 2,5-substituted piperidines, substituted methylene diamines, substituted imidazolidines and the like.
[0068]
Specific examples of the oxygen-containing compound include 2,6-substituted tetrahydropyrans and 2,5-substituted tetrahydropyrans.
Specific examples of phosphorus-containing compounds include phosphites.
[0069]
These electron donors (F) can be used singly or in combination of two or more.
[0070]
Examples of olefins that can be polymerized using such an olefin polymerization catalyst include α-olefins having 2 to 20 carbon atoms, such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4- Mention may be made of methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene and the like.
[0071]
In the polymerization, these olefins can be used alone or in combination. Furthermore, aromatic vinyl compounds such as styrene and allylbenzene, alicyclic vinyl compounds such as vinylcyclohexane, cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl-1,4,5 , 8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene and other cyclic olefins, 6-methyl 1,6-octadiene, 7-methyl-1,6-octadiene, 6- Ethyl-1,6-octadiene, 6-propyl-1,6-octadiene, 6-butyl-1,6-octadiene, 6-methyl-1,6-nonadiene, 7-methyl-1,6-nonadiene, 6- Ethyl-1,6-nonadiene, 7-ethyl-1,6-nonadiene, 6-methyl-1,6-decadiene, 7-methyl-1,6-decadiene, 6-methyl-1,6-undecadiene, isoprene, Polymers containing polyunsaturated compounds such as conjugated and non-conjugated dienes such as butadienes and other dienes It can also be used as.
[0072]
The polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization or a gas phase polymerization method.
[0073]
In the polymerization, the (a) solid titanium catalyst component is generally about 0.0001 to 50 mmol, preferably about 0, in terms of the titanium atom in the (a) solid titanium catalyst component per liter of polymerization volume. Used in an amount of .001 to 10 mmol. In addition, (b) the organoaluminum catalyst component is usually about 1 to 2000 mol, preferably about 2 to 500 mol, of aluminum atom contained in (b) the organoaluminum catalyst component with respect to 1 mol of titanium atom in the polymerization system. Is used in such an amount that Further, (c) the organosilicon compound is used in an amount of usually about 0.001 to 50 moles, preferably about 0.01 to 20 moles per mole of aluminum atoms in the (b) organoaluminum catalyst component. .
[0074]
When hydrogen is used during the polymerization, a polyolefin having a high melt flow rate can be obtained, and the molecular weight of the obtained polyolefin can be adjusted by the amount of hydrogenation.
[0075]
When the liquid phase polymerization method is used for the reaction conditions, the polymerization temperature is usually about −50 to 200 ° C., preferably about 20 to 100 ° C., and the polymerization pressure is usually normal pressure to 100 kg / cm.², Preferably about 2-50 kg / cm²Set to When performing the gas phase polymerization method, the polymerization temperature is usually about −50 to 200 ° C., preferably about 20 to 100 ° C., and the polymerization pressure is usually atmospheric pressure to 100 kg / cm 2.², Preferably about 2-50 kg / cm²Set to
[0076]
The polymerization can be carried out by any of batch, semi-continuous and continuous methods.
[0077]
【The invention's effect】
In the preparation method of the solid titanium catalyst component of the present invention, when preparing the solid titanium catalyst component, 88 to 99% by weight of a titanium compound as a solution-like titanium compound and 1 to 1 hydrocarbon containing a halogen-containing hydrocarbon are used. Since the titanium compound mixed solution containing 12% by weight is used, a solid titanium catalyst component for olefin polymerization having high activity per unit catalyst can be obtained.
[0078]
Further, in the step of bringing the solution-like magnesium compound and the solution-like titanium compound into contact with each other, the solution containing the titanium compound not supported on the solid product and / or the solid product and the solution-like titanium compound are brought into contact with each other. When a solution containing the titanium compound not supported on the solid titanium catalyst component in the process is distilled and used as a titanium compound mixture, the titanium compound can be reused and economically advantageous. It is.
[0079]
Since the polyolefin production method of the present invention uses the olefin polymerization catalyst containing the solid titanium catalyst component as described above, the olefin can be polymerized with high polymerization activity.
[0080]
【Example】
EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.
[0081]
In this example, the composition of the titanium tetrachloride mixed liquid was measured by measuring the separated hydrocarbons by gas chromatography using an apparatus as shown in FIG. The purity of titanium tetrachloride was obtained by subtracting the weight of hydrocarbon from the weight of the titanium tetrachloride mixed solution as the weight of titanium tetrachloride. FIG. 2 is a schematic explanatory view showing an apparatus used for determining the composition of the titanium tetrachloride mixed solution, wherein 1 is a condenser, 2 is a round bottom flask, 3 is ice water, 4 is a cooling water circulation pump, and 5 is a peristor. Pump 6 indicates a stirrer.
(1) About 20 ml of toluene is put into a dry 200 ml round bottom flask.
(2) Collect 10 ml of sample with a whole pipette and put into a round bottom flask.
(3) Connect the flask and condenser as shown in Fig. 2 and cool with ice.
(4) Turn on the cooling water circulation pump to circulate ice water in the condenser.
(5) When the condenser cools, switch on the peristaltic pump and start dripping pure water at a rate of 2 ml per minute. (SPEED = × 15, CONTROL = 3-5, POWER = R)
(6) When water is added dropwise, a tan solid is produced. In this state, hold the joint between the flask and the condenser with your hand and stir slowly. (A stirrer may be set and stirred.)
(7) When water is further added dropwise, the solid substance dissolves and becomes a cloudy liquid. The reaction ends when the cloudiness disappears.
(8) Transfer the contents of the round bottom flask to a 100 ml separatory funnel A, wash the inner wall of the round bottom flask with 10 ml of toluene, and transfer to the separatory funnel A.
(9) Shake the separatory funnel A, and after standing and separating, transfer the aqueous phase to another separatory funnel B, and transfer the toluene phase to a 50 ml volumetric flask.
(10) Put 10 ml of toluene in the separatory funnel A, wash the inner wall, transfer to the separatory funnel B, and shake.
(11) After stationary separation, the toluene phase is put into a 50 ml volumetric flask containing toluene.
(12) About 0.5 ml of p-xylene was added to a 50 ml volumetric flask containing the toluene phase, and gas chromatography was measured under the following conditions.
[0082]

[0083]
[Example 1]
Preparation of solid titanium catalyst component (A-1)
0.5m^ThreeInto the reactor, 98.5 kg of 2-ethylhexyl alcohol, 78.3 kg of decane, and 24 kg of magnesium chloride were charged, and a homogeneous solution was prepared at 140 ° C., followed by 5.6 kg of phthalic anhydride. The liquid magnesium compound (m-1) was obtained by cooling to room temperature.
[0084]
Next, 1m^ThreeA titanium tetrachloride mixed solution (1) having a composition shown in Table 1 in a reactor of 0.3 m^ThreeThe temperature was lowered at −20 ° C., and 103.2 kg of the magnesium compound (m-1) was charged. This titanium tetrachloride mixed liquid (1) is composed of a hydrocarbon containing titanium tetrachloride stored in the storage tank (D) in Comparative Example 2 below, at a bottom temperature of 67.5 ° C., a top temperature of 52.0 ° C., and a top pressure of 50 Torr. It was obtained by distillation under conditions of a reflux amount of 500.1 kg / hour.
[0085]
After the completion of charging, the temperature was raised to 110 ° C., and 8.8 kg of diisobutyl phthalate was charged and held for 2 hours. After completion of the reaction, the liquid phase part was extracted and stored in the storage tank (D), and the solid part was pressure-fed with a nitrogen filter and filtered.
[0086]
Add a small amount of titanium tetrachloride to the solid part after filtration and add 1m^Three0.4m to the reactor^ThreeThe titanium tetrachloride mixed liquid (1) having the composition shown in Table 1 was added.
The filter is 100 ° C, 1m with felter^ThreeThe pressure feed line connecting the reactors was maintained at 90 ° C.
[0087]
Next, 1m^ThreeAfter the temperature in the reactor was raised to 110 ° C. and held for 20 minutes, the liquid phase part was pressure-fed to a filter in the same manner as above and filtered. 1m after filtration^ThreeThe reactor was pumped to 60 ° C hexane 0.4m^ThreeAfter repeating the washing with 3 times, washing with hexane at room temperature was carried out until no titanium was detected in the supernatant.
[0088]
The solid part thus obtained was dried with a paddle dryer to obtain a solid titanium catalyst component (A-1) having a composition as shown in Table 2.
polymerization
An autoclave with an internal volume of 2 liters was charged with 750 ml of purified n-hexane, 0.75 mmol of triethylaluminum, 0.075 mmol of cyclohexylmethyldimethoxysilane and a solid titanium catalyst component (A-1) in a propylene atmosphere at 40 ° C. Was charged with 0.0075 mmol Ti in terms of titanium atoms.
[0089]
Further, 200 ml of hydrogen was introduced at 60 ° C., the temperature was raised to 70 ° C., and this was maintained for 2 hours to carry out propylene polymerization. Pressure during polymerization is 7 kg / cm²-G kept.
After the polymerization was completed, the slurry containing the produced solid was filtered and separated into a white powder and a liquid phase part, and then the white powder was dried under reduced pressure for 10 hours, and the weight and physical properties were measured. Further, a part of the liquid phase part was concentrated, and the amount of polymer soluble in the solvent (n-hexane) was calculated. The results are shown in Table 3.
[0090]
[Example 2]
Preparation of solid titanium catalyst component (A-2)
The titanium compound-containing solution (purity of titanium tetrachloride 85% by weight) stored in the storage tank (D) obtained in Example 1 was subjected to bottom temperature 68.3 ° C, top temperature 52.6 ° C, top pressure 46 Torr, reflux. Distillation was carried out under the condition of an amount of 479.2 kg / hour to obtain a titanium tetrachloride mixed solution (2) having the composition shown in Table 1.
[0091]
The solid titanium catalyst component (A-2) was prepared in the same manner as in Example 1 except that this titanium tetrachloride mixed liquid (2) was used instead of the titanium tetrachloride mixed liquid (1) used in Example 1. Prepared. Table 2 shows the composition of the solid titanium catalyst component (A-2).
[0092]
polymerization
In Example 1, propylene was polymerized in the same manner as in Example 1 except that the solid titanium catalyst component (A-2) was used instead of the solid titanium catalyst component (A-1). The results are shown in Table 3.
[0093]
[Example 3]
Preparation of solid titanium catalyst component (A-3)
The titanium compound-containing solution (purity of titanium tetrachloride 85% by weight) stored in the storage tank (D) obtained in Example 2 was subjected to a bottom temperature of 70.2 ° C., a top temperature of 54.3 ° C., a top pressure of 52 Torr, and reflux. Distillation was carried out under the condition of an amount of 449.8 kg / hour to obtain a titanium tetrachloride mixed solution (3) having the composition shown in Table 1.
[0094]
The solid titanium catalyst component (A-3) was prepared in the same manner as in Example 1 except that this titanium tetrachloride mixed solution (3) was used instead of the titanium tetrachloride mixed solution (1) used in Example 1. Prepared. Table 2 shows the composition of the solid titanium catalyst component (A-3).
[0095]
polymerization
Propylene was polymerized in the same manner as in Example 1 except that instead of the solid titanium catalyst component (A-1) in Example 1, the solid titanium catalyst component (A-3) was used. The results are shown in Table 3.
[0096]
[Example 4]
Preparation of solid titanium catalyst component (A-4)
The titanium compound-containing solution (purity of titanium tetrachloride 85% by weight) stored in the storage tank (D) obtained in Example 3 was subjected to bottom temperature 67.1 ° C., top temperature 49.2 ° C., top pressure 30 Torr, reflux. Distillation was carried out under the condition of an amount of 481.7 kg / hour to obtain a titanium tetrachloride mixed solution (4) having the composition shown in Table 1.
[0097]
The solid titanium catalyst component (A-4) was prepared in the same manner as in Example 1 except that this titanium tetrachloride mixed solution (4) was used instead of the titanium tetrachloride mixed solution (1) used in Example 1. Prepared. Table 2 shows the composition of the solid titanium catalyst component (A-4).
[0098]
polymerization
In Example 1, propylene was polymerized in the same manner as in Example 1 except that the solid titanium catalyst component (A-4) was used instead of the solid titanium catalyst component (A-1). The results are shown in Table 3.
[0099]
[Example 5]
Preparation of solid titanium catalyst component (A-5)
The titanium compound-containing solution (purity of titanium tetrachloride 85% by weight) stored in the storage tank (D) obtained in Example 4 was subjected to bottom temperature 69.6 ° C., top temperature 52.8 ° C., top pressure 47 Torr, reflux. Titanium tetrachloride mixed solution (5) having the composition shown in Table 1 by mixing an equal amount of a solution distilled in a condition of 480.7 kg / hour and a titanium compound-containing solution stored in storage tank (D). Got.
[0100]
The solid titanium catalyst component (A-5) was prepared in the same manner as in Example 1 except that this titanium tetrachloride mixed solution (5) was used instead of the titanium tetrachloride mixed solution (1) used in Example 1. Prepared. Table 2 shows the composition of the solid titanium catalyst component (A-5).
[0101]
polymerization
In Example 1, propylene was polymerized in the same manner as in Example 1 except that the solid titanium catalyst component (A-5) was used instead of the solid titanium catalyst component (A-1). The results are shown in Table 3.
[0102]
[Comparative Example 1]
Preparation of solid titanium catalyst component (A-6)
The titanium compound-containing solution (titanium tetrachloride purity 85% by weight) stored in the storage tank (D) obtained in Example 1 was not distilled and replaced with the titanium tetrachloride mixture (1) used in Example 1. A solid titanium catalyst component (A-6) was prepared in the same manner as in Example 1 except that it was used. Table 2 shows the composition of the solid titanium catalyst component (A-6).
[0103]
polymerization
In Example 1, propylene was polymerized in the same manner as in Example 1 except that the solid titanium catalyst component (A-6) was used instead of the solid titanium catalyst component (A-1). The results are shown in Table 3.
[0104]
[Comparative Example 2]
Preparation of solid titanium catalyst component (A-7)
A solid titanium catalyst component (A-7) was used in the same manner as in Example 1 except that 100% by weight of titanium tetrachloride was used instead of the titanium tetrachloride mixed liquid (1) used in Example 1. Was prepared. Table 2 shows the composition of the solid titanium catalyst component (A-7).
[0105]
polymerization
In Example 1, propylene was polymerized in the same manner as in Example 1 except that the solid titanium catalyst component (A-7) was used instead of the solid titanium catalyst component (A-1). The results are shown in Table 3.
[0106]
[Example 6]
Preparation of solid titanium catalyst component (A-8)
A four-necked flask equipped with a stirrer was thoroughly purged with nitrogen, and 4.8 g of magnesium chloride was added at room temperature (26 ° C.). Next, 75 ml of toluene was added, stirring was started at 200 rpm, 7.85 ml of chloromethyloxirane was added, and 8.18 ml of tri-n-butyl phosphate was further added. Next, the stirring number was 350 rpm and the temperature was raised to 50 ° C. After maintaining at 50 ° C. for 2 hours, 1.18 g of phthalic anhydride was added, and further maintained at 50 ° C. for 1 hour to obtain a liquid magnesium compound (m-2).
[0107]
Next, after cooling to −23 ° C., the same titanium tetrachloride mixed solution (1) as that used in Example 1 was dropped at the same temperature for 1 hour. Next, the temperature was raised to 80 ° C. over 4 hours, and 3.35 ml of diisobutyl phthalate was added. After maintaining at the same temperature for 1 hour, the solid part was collected by filtration, and the obtained solid part was washed twice with 100 ml of toluene.
[0108]
The solid part after washing was suspended in 60 ml of toluene, returned to the flask, added with 40 ml of a titanium tetrachloride mixed liquid (1), and then heated to 90 ° C. After maintaining at 90 ° C. for 1 hour, the solid portion was collected by filtration, resuspended in 60 ml of toluene, and returned to the flask. Next, after adding the titanium tetrachloride mixed liquid (1), the temperature was raised to 90 ° C. and held for 1 hour, and then the solid part was collected by filtration. The obtained solid part was washed with 100 ml of 1,2-dichloroethane and then washed 4 times with 100 ml of hexane to obtain a solid titanium catalyst component (A-8). Table 2 shows the composition of the solid titanium catalyst component (A-8).
[0109]
polymerization
In Example 1, propylene was polymerized in the same manner as in Example 1 except that the solid titanium catalyst component (A-8) was used instead of the solid titanium catalyst component (A-1). The results are shown in Table 3.
[0110]
[Comparative Example 3]
Preparation of solid titanium catalyst component (A-9)
A solid titanium catalyst component (A-9) was used in the same manner as in Example 6 except that titanium tetrachloride having a purity of 100% by weight was used instead of the titanium tetrachloride mixed solution (1) used in Example 6. Was prepared. Table 2 shows the composition of the solid titanium catalyst component (A-9).
[0111]
polymerization
In Example 1, propylene was polymerized in the same manner as in Example 1 except that the solid titanium catalyst component (A-9) was used instead of the solid titanium catalyst component (A-1). The results are shown in Table 3.
[0112]
[Table 1]

[0113]
[Table 2]

[0114]
[Table 3]

[Brief description of the drawings]
FIG. 1 is an explanatory diagram showing an example of a method for preparing a solid titanium catalyst component according to the present invention.
FIG. 2 is a schematic explanatory view showing an apparatus used when determining the composition of a titanium tetrachloride mixed solution.
[Explanation of symbols]
1 ... Condenser
2… round bottom flask
3 ... ice water
4 ... Cooling water circulation pump
5 ... Peristaltic pump
6 ... Stirrer

Claims (4)

In preparing a solid titanium catalyst component containing titanium, magnesium and halogen as essential components by contacting (A) a magnesium compound and (B) a solution-like titanium compound,
(B) A solid for olefin polymerization using a titanium compound mixed solution composed of 88 to 99% by weight of a titanium compound and 1 to 12% by weight of a hydrocarbon containing a halogen-containing hydrocarbon as the solution-like titanium compound Of preparing a titanium catalyst component. (A ′) a solid component produced by bringing a solution-like magnesium compound and (B) a solution-like titanium compound into contact with each other in the presence of (C) an electron donor, supporting a polyvalent carboxylic acid ester, When preparing a solid titanium catalyst component containing titanium, magnesium, halogen and a polyvalent carboxylic acid ester as essential components,
(B) A solid for olefin polymerization using a titanium compound mixed solution composed of 88 to 99% by weight of a titanium compound and 1 to 12% by weight of a hydrocarbon containing a halogen-containing hydrocarbon as the solution-like titanium compound Of preparing a titanium catalyst component. (A ') Formed by supporting polyvalent carboxylic acid ester on solid component produced by contacting solution-like magnesium compound and (B) solution-like titanium compound in the presence of (C) electron donor. In preparing a solid titanium catalyst component containing titanium, magnesium, halogen and polyvalent carboxylic acid ester as essential components by bringing the solid product thus obtained into contact with (B ′) a solution-like titanium compound.
Titanium compound comprising 88 to 99% by weight of a titanium compound and 1 to 12% by weight of a hydrocarbon containing a halogen-containing hydrocarbon as the (B) solution-like titanium compound and / or the (B ′) solution-like titanium compound. A method for preparing a solid titanium catalyst component for olefin polymerization, which comprises using a mixed solution. (A) a solid titanium catalyst component obtained by the method according to claims 1 to 3;
(B) an organoaluminum catalyst component;
(C) A method for producing a polyolefin, comprising using an olefin polymerization catalyst comprising an organosilicon compound catalyst component having a Si—O—C bond.

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